TEM evidence of perovskite–brownmillerite coexistence in the Ca(AlxFe1−x)O2.5 system with minor amounts of titanium and silicon

Observations by transmission electron microscopy (TEM) of the submicrometer phases present in calcium aluminate cements have shown that Ca-Al-Fe oxides coexist in two forms with brownmillerite (b) and perovskite (p) structures, respectively. Homogeneous single crystals of both brownmillerite and perovskite have been observed but exsolved lamellae also occur on the scale of tens of nanometers. Perovskite lamellae in brownmillerite exhibit coherent interfaces with an almost perfect [1 0 1]_b = {1 0 0}_p topotactic relationship. Energy-dispersive X-ray spectroscopy (EDXS) measurements show that perovskite lamellae are enriched in Ti and Si relative to the brownmillerite lamellae. The perovskite phase may accommodate up to 0.17 Si atoms per formula unit, but the exsolution process seems mainly to concern the Ti content. It is estimated that the solvus width ranges between concentrations of 0.06 < Ti < 0.13 atoms per formula unit. O K and Fe L _2,3 edges collected by electron energy loss spectrometry (EELS) confirm that both phases are mainly composed of Fe³⁺, requiring that the perovskite is highly oxygen-deficient. Al K and Si K EELS spectra have features comparable with those of fourfold-co-ordinated Al and Si sites, suggesting that they are probably located close to oxygen-vacant sites. Received: 23 June 1999 / Accepted: 18 February 2000     

Fe2+-Mg order-disorder in orthopyroxene: equilibrium fractionation between the octahedral sites and thermodynamic analysis

The equilibrium intracrystalline distribution coefficient, k _D ^*, of Fe^* (i.e. Fe²⁺ + Mn) and Mg between the M1 and M2 sites of three natural nearly binary Fe²⁺-Mg orthopyroxene crystals (Fs₁₄, Fs₁₅ and Fs₄₉) were determined by annealing experiments at several temperatures between 550 and 1000 °C and single crystal X-ray structure refinements. In addition, the X-ray data of an orthopyroxene crystal (Fs₂₃), which were collected earlier by Molin et al. (1991) between 700 and 1000 °C, were re-refined. The data were processed through two different refinement programs (SHELXL-93 and RFINE90) using both unit and individual weights and also both ionic and atomic scattering factors. The calculated site occupancies were found to agree within their estimated standard errors. However, the use of ionic scattering factors led to significantly better goodness of fit and agreement index, and smaller standard deviations of the site occupancies than those obtained from the use of atomic scattering factors. Furthermore, the weighted refinements yielded significantly smaller standard deviations of the site occupancies than the unweighted refinements even when the same set of reflections was used in the two procedures. The site occupancy data from this study were combined with selected published data to develop expressions of k _D ^* as a function of temperature and composition. Calculation of the excess configurational entropy, ΔS ^XS, suggests that orthopyroxene should be treated as a two parameter symmetric solution instead of as a “simple mixture”. The calculated ΔS ^XS values and the excess Gibbs free energy of mixing suggested by available cation exchange data lead to a slightly negative enthalpy of mixing in the orthopyroxene solid solution. Received: 25 August 1998 / Accepted: 10 March 1999     

Luna 20 pyroxenes: exsolution and phase transformation as indicators of petrologic history

Pyroxenes from our sample of Luna 20 soil are predominantly orthopyroxene with subordinate pigeonite. The orthopyroxenes are chromium-rich bronzites and contain submicroscopic lamellae of augite in a twinned orientation exsolved on (100). These lamellae have a composition close to the diopside-hedenbergite join. Asymmetric diffuse streaks parallel to $\text{a}{}^1$ indicate stacking faults parallel to (100) and possibly very thin (10–20 Å) lamellae of clinobronzite parallel to (100). Pigeonite crystals are very complex crystallographically and chemically, with optically visible (001) augite exsolution lamellae and two sets of chromite exsolution lamellae. In addition, there are submicroscopic (100) augite lamellae and a second generation of clinohypersthene lamellae which appear to have exsolved from the (001) augite lamellae. The clinohypersthene host, which has a large number of stacking faults parallel to (100), has partially inverted to hypersthene of the same composition. The hypersthene occurs as very fine lamellae (less than 1000 Å) parallel to the (100) plane of the clinohypersthene. X_D^Fe-Mg values for five host-lamellae pairs in pigeonite K-4 indicate a significant amount of subsolidus readjustment. We tentatively conclude that many of the bronzite and pigeonite crystals were derived from rocks crystallized from a high level magma chamber in the lunar highland crust.     

Formation mechanism of pigeonite lamellae in skaergaard augite

Fine textures of exsolution lamellae and interface boundaries between augite and pigeonite in augite crystals from Skaergaard ferrogabbro 4430 have been studied by high resolution electron microscopy and X-ray methods. Thick pigeonite lamellae have higher densities of (100) stacking faults than thin lamellae. The displacement vector of the faults has been determined as 5/6c from the measured density of faults and the relative rotation of the augite and pigeonite lattices. The augite and pigeonite lattices are apparently coherent, and no growth ledges were observed at the interfaces. The stacking faults are often combined with the antiphase boundary of pigeonite resulting in a total displacement vector of 1/2(a+b)+5/6c. The observation of thick and thin pigeonite lamellae indicated that the thickening of (001) pigeonite lamellae was controlled by coherency strains accumulated at the interfaces between augite and pigeonite.     

Magnetite, ilmenite and ulvite in rocks and ore deposits: petrography, microprobe analyses and genetic implications

Summary ?Detailed petrographic studies and microchemical analyses of titanomagnetite from igneous and metamorphic rocks and ore deposits form the basis of this investigation. Its aim is to compare the data obtained and their interpretations with the experimentally deduced subsolidus oxidation-exsolution model of Buddington and Lindsley (1964). The results are also considered relevant for the interpretation of compositional variations in black sands which are recovered for titanium production. The arrangement of the samples investigated is in accordance with textural stages C1 to C5 caused by subsolidus exsolution with increasing degrees of oxidation (Haggerty, 1991). Stage 1 is represented by two types of optically homogeneous TiO₂-rich magnetite: a. An isotropic type considered to represent solid solutions of magnetite and ulvite containing between 5.2 to 27.5 wt% TiO₂ corresponding to about 14.7 to 77.7 mol% Fe₂TiO₄ in solid solution with magnetite. The general formula of this type is Fe²⁺ _1+x Fe³⁺ _2−2x Ti _x O₄ (x = 0.0–1.0). b. The second type which has not been reported so far is anisotropic and shows complex internal twinning resembling inversion textures. It is thus attributed to inversion of a high-temperature ilmenite modification (with statistical distribution of the cations) which forms solid solutions with magnetite. TiO₂ varies between 9.3 and 24.5 wt% corresponding to about 17.2 to 43.6 mol% ilmenite in solid solution with magnetite. This type is interpreted as a cation-deficient spinel with the general formula Fe²⁺ _{12/12 + 1/4x}Fe³⁺ _{24/12 − 3/2x} □ _{0 + 1/4x} Ti _x O₄ (x = 0.0–16/12). Isotropic and anisotropic homogeneous magnetites occur in volcanic rocks only; the homogeneity of the solid solutions was explained by fast cooling which prevented the development of exsolution textures. Stages 2 and 3 are represented by magnetite with or without ulvite. The magnetite host contains ilmenite lamellae forming trellis and sandwich textures. In contrast to the requirement of the oxidation-exsolution model, the ilmenite lamellae are concentrated exclusively in the cores of the host crystals. The reverse host-guest relationship may also occur. Stages 4 and 5 are identical with thermally generated martite (= martite due to heating). The textures are characterized by very broad lamellae of ferrian ilmenite or titanohematite dominantly concentrated along the margins of the host crystals. Thermally generated martite is restricted to subsolidus-oxidation reactions. The ilmenite lamellae of trellis and sandwich textures contain low Fe₂O₃-concentrations (average 4.8 mol%; to a maximum of 8.3), whereas the Fe₂O₃-content of thermally generated martite is between 32 to 71 mol%. With respect to the Fe₂O₃-concentrations in the ilmenite lamellae, no transition between the two types was observed. The results of this paper show that the widely accepted oxy-exsolution model of Buddington and Lindsley (1964) which is based on experimental results can – with the exception of thermally generated martite – not explain the tremendous variety of magnetite–ilmenite–ulvite relationships in natural rocks and ore deposits. Received October 16, 2001; accepted May 2, 2002     

Exsolution in augite from the Skaergaard Intrusion

The exsolution phenomena of augite from Ferrogabbro 4430 of the Skaergaard Intrusion were examined in detail by single crystal X-ray diffraction and heating experiments to study the stepwise exsolution process. In the augite crystals, five different phases were detected: pigeonite (001), pigeonite (100), orthopyroxene (a), orthopyroxene (p) and a small amount of clinoamphibole. The two different pigeonites nearly share the corresponding (001) and (100) planes with the host. Orthopyroxene (a) and orthopyroxene (p) have (100) in common with the host and with exsolved pigeonite (001), respectively. Clinoamphibole was observed in the form of rather weak reflections in many crystals. It has (010) in common with the host.A large number of augite crystals exhibited a pigeonite (001) phase with curved, rotated reflections and diffuse streaks along the a* direction in (h0l) precession photographs. It appears that these streaks are related to orthopyroxene (p). Orthopyroxene (p) seems to be crystallized from pigeonite (001) by nucleation at (100) stacking fault planes (inverted pigeonite). Pigeonite (100) may be formed at growth ledges between augite host and exsolved orthopyroxene (a) at a later stage of exsolution to stabilize the boundaries.From the X-ray diffraction profiles and the results of the heating experiments, a possible exsolution sequence is suggested. Clinoamphibole appears to be a product of alteration at the latest stage of the exsolution process. It seems to be related to particular conditions of partial water pressure.     

Equilibrium coexistence of three amphiboles

Electron probe and wet chemical analyses of amphibole pairs from the sillimanite zone of central Massachusetts and adjacent New Hampshire indicated that for a particular metamorphic grade there should be a restricted composition range in which three amphiboles can coexist stably. An unequivocal example of such an equilibrium three amphibole rock has been found in the sillimanite-orthoclase zone. It contains a colorless primitive clinoamphibole, space group P2₁/m, optically and chemically like cummingtonite with blue-green hornblende exsolution lamellae on (100) and (¯101) of the host; blue-green hornblende, space group C2/m, with primitive cummingtonite exsolution lamellae on (100) and (¯101) of the host; and pale pinkish tan anthophyllite, space group Pnma, that is free of visible exsolution lamellae but is a submicroscopic intergrowth of two orthorhombic amphiboles. Mutual contacts and coarse, oriented intergrowths of two and three host amphiboles indicate the three grew as an equilibrium assemblage prior to exsolution. Electron probe analyses at mutual three-amphibole contacts showed little variation in the composition of each amphibole. Analyses believed to represent most closely the primary amphibole compositions gave atomic proportions on the basis of 23 oxygens per formula unit as follows: for primitive cummingtonite (Na_0.02Ca_0.21 ^– Mn_0.06Fe²⁺ _2.28Mg_4.12Al_0.28) (Al_0.17Si_7.83), for hornblende (Na_0.35Ca_1.56Mn_0.02Fe_1.71Mg_2.85Al_0.92) (Al_1.37Si_6.63), and for anthophyllite (Na_0.10Ca_0.06Mn_0.06Fe_2.25Mg_4.11Al_0.47) (Al_0.47Si_7.53). The reflections violating C-symmetry, on X-ray single crystal photographs of the primitive cummingtonite, are weak and diffuse, and suggest a partial inversion from a C-centered to a primitive clinoamphibole. Single crystal photographs of the anthophyllite show split reflections indicating it is an intergrowth of about 80% anthophyllite and about 20% gedrite which differ in their b crystallographic dimensions. Split reflections are characteristic of all analyzed orthorhombic amphiboles so far examined from Massachusetts and New Hampshire except the most aluminous gedrites, and the relative intensity of the gedrite reflections is roughly proportional to the degree of Na and Al substitution. Thin sections of a few of these anthophyllite specimens show lamellae parallel to (010) that are just resolved with a high power objective.Publication approved by the Director, U.S. Geological Survey.     

Unusual exsolution phenomena in omphacite and partial replacement of phengite by phlogopite + kyanite in an eclogite from the Erzgebirge

In the Erzgebirge Crystalline Complex, eclogites occur in three different high pressure (HP) units (1, 2 and 3) recording contrasting pressure (P)–temperature (T) conditions. Eclogites from HP-unit 1 experienced peak metamorphic conditions in the coesite stability field at about 33 kbar/850 °C. Commonly, these eclogites from HP-unit 1 are all very similar, with an eclogitic peak assemblage of omphacite–garnet–coesite–K-feldspar, rarely accompanied by kyanite, and omphacites systematically deviating from a stoichiometric composition. In contrast, an eclogite recently found near Blumenau, is mineralogically and geochemically different from the typical eclogites of HP-unit 1. This unusual eclogite reveals the eclogitic equilibrium assemblage omphacite–garnet–coesite–phengite–phlogopite–kyanite, and yields metamorphic peak conditions of 870 °C and >29 kbar. There is clear textural evidence of the formation of phlogopite and kyanite under partial consumption of phengite and garnet. Moreover, the omphacite is stoichiometric and contains abundant exsolution lamellae, the thickest of which were identified as quartz by the electron microprobe. The finer lamellae were studied by transmission electron microscopy (TEM). Oligoclase was identified as an exsolution phase. Other lamellae proved to consist of K-white mica, also interpreted as exsolution. Prior to exsolution, the omphacite composition must have been cation-deficient, as that of the other, common HP-unit 1 eclogites. These non-stoichiometric compositions are ascribed to partial substitution by the Ca-Eskola pyroxene component, which calculates to an average of 8 mol% for omphacite in HP-unit 1 eclogites. According to experiments, this substitution becomes significant at P > 30 kbar. Exsolution of K-white mica may indicate hydroxyl defects in the original omphacite, also favoured by high pressure. Oligoclase and K-white mica exsolution from Ca-Eskola-rich clinopyroxene has not previously been reported. The omphacite has a disordered C2/c structure; and in just one case very small (a few tens of nanometres) antiphase domains, resulting from the C2/c to P2/n transformation, are present. These features may indicate a brief thermal history and rapid tectonic processes. Received: 4 January 1999 / Accepted: 20 April 2000     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

Microanalysis of Fe3+/ΣFe in oxide and silicate minerals by investigation of electron energy-loss near-edge structures (ELNES) at the Fe M 2,3 edge

The Fe M _2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe₃(Al_1–xFe_x)₂[SiO₄]₃ and andradite-skiagite (Fe_1–xCa_x)₃Fe₂[SiO₄]₃), pyroxenes (acmite-hedenbergite (Ca_1–xNa_x)(Fe²⁺ _1−xFe³⁺ _x)Si₂O₆), and spinels (magnetite-hercynite Fe(Al_1–xFe_x)₂O₄) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M _2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe³⁺/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe³⁺/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M _2,3 edge is observed. Since the partial cross sections of the Fe M _2,3 edges are some orders of magnitude higher than those of the Fe L _2,3 edges, the Fe M _2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M _2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe³⁺/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999     

The crystal structure of an aluminum-rich schorl overgrown by boron-rich olenite from Koralpe, Styria, Austria

Summary The first natural tourmaline (because tourmaline with ^[4]B has also been synthesized, we distinguish here between natural and synthetic tourmaline) that has been unequivocally demonstrated to contain B as a substituent at the T sites was described from Koralpe, Styria, Austria. This colourless B-rich olenite occurs as rims overgrowing schorl (black crystals up to a few cm) that has not yet been structurally characterized. A crystal structure refinement (R = 0.019) of this Al-rich schorl shows that ^[4]B occurs in the overgrown schorl; the optimized occupants of the atomic positions yield ^X (Na_0.64Ca_0.10K_0.06□_0.20) ^Y (Fe²⁺ _1.72Al_1.08Ti_0.11Zn_0.03□_0.06) ^Z (Al_5.70Mg_0.20Fe_0.08 ²⁺Mn_0.02) (^[3]BO₃)_3.00 ^T (Si_5.76 ^[4]B_0.24)O₁₈ [F_0.11(OH)_3.31O_0.58]. This is the first known (Al-rich) schorl where a structure refinement has detected ^[4]B. Comparing the structure refinements and the chemical composition of the Koralpe schorl and other ^[4]B-bearing tourmalines with tourmalines which contain no ^[4]B, it is of interest that only structure refinements of tourmalines which are low in magnesium and with a higher component of olenite show substantial amounts of ^[4]B; the role of Mg in controlling the amount of ^[4]B is not known, but it seems that an Al-component on the Y site (olenite-component), a boron-enriched environment and special P-T-t conditions are necessary to get tourmaline with substantial amounts of ^[4]B. Received July 7, 2000; revised version accepted June 6, 2001     

Observation of reactions in synthetic Ca-poor pyroxene single crystals at elevated temperatures by X-ray diffraction

Diffuse streaks in diffraction patterns of synthetic pyroxene single crystals at elevated temperatures are used to determine which reactions are initiated and how they proceed. The samples investigated are a) a host orthopyroxene (Wo₄En₈₃Fs₁₃) containing oriented pigeonite (Wo₆En₇₈Fs₁₆) parallel to (100) and b) a pigeonite (Wo₈En₇₅Fs₁₇). The maximum temperatures were 820° C and 1,015° C, respectively. No partial melting occurs at these temperatures, all reactions are in the subsolidus. In case a) augite is formed parallel to the (001) plane of pigeonite, but the augite is not exsolved by the pigeonite. This is proved by the absence of the obligatory streaks between corresponding reflections in highly resolved precession photographs. Instead, there are streaks from augite to the corresponding reflections of the host orthopyroxene. Example b) demonstrates that the temperature of the high-low transformation of pigeonite is very sensitive to the Ca content and clearly depends on the exsolution of augite. This augite is oriented parallel to (100) of pigeonite, not to (001). Both the high and the low pigeonite are present over a range of ～150° C, while the exsolution of augite continues. Simultaneously, orthopyroxene is also formed sharing (100) of pigeonite. There seems to be an indication that only low pigeonite inverts to orthopyroxene.     

Valence state mapping and quantitative electron spectroscopic imaging of exsolution in titanohematite by energy-filtered TEM

 The microstructure of hematite-ilmenite exsolution intergrowth of a natural titanohematite crystal from a granulite has been investigated in a transmission electron microscope equipped with an energy filter. Special emphasis is on quantitative compositional mapping at the nanometre scale using electron spectroscopic imaging, as well as mapping the Fe³⁺ and Fe²⁺ valence distribution in the intergrowth. Quantitative point analyses by energy-dispersive X-ray analysis have been compared with results from electron energy-loss spectroscopy and element-distribution mapping. The results indicate that the coexisting compositions of the two phases (Ilm₈₈Hem₁₂ and Ilm₁₆Hem₈₄) are independent of the size of the exsolution. The application of quantitative mapping to determining diffusion profiles around precipitates is demonstrated. Received: 30 March 2000 / Accepted: 7 September 2000     

Displacive phase transitions in C-centred clinopyroxenes: spodumene, LiScSi2O6 and ZnSiO3

The clinopyroxenes spodumene (LiAlSi₂O₆), LiScSi₂O₆ and ZnSiO₃, all with space group C2/c at ambient conditions, were studied under high pressures by single-crystal X-ray diffraction in a diamond-anvil cell. Changes in the evolution of the unit-cell parameters, optical properties and the appearance of h + k odd reflections characteristic of a primitive lattice, indicate that all three pyroxenes undergo phase transitions. The transitions are mostly displacive in character, and are non-quenchable. Transition pressures are 3.19 GPa in spodumene, ∼0.6 GPa in LiScSi₂O₆ and 1.92 GPa in ZnSiO₃. The space group of all three high-pressure phases was determined to be P2₁/c by structure refinement to single-crystal X-ray intensity data collected in the DAC. In the ZnSiO₃ clinopyroxene the intermediate P2₁/c phase further transforms to a second C2/c phase (HP-C2/c) at 4.9 GPa (confirmed by structure refinement). The volume change at this transition is about 2.6%, three times larger than in the first phase transition, and typical of the P2₁/c→ HP-C2/c phase transitions found previously in MgSiO₃, FeSiO₃, etc. These results therefore provide the first direct evidence that the HP-C2/c and the HT-C2/c structures of pyroxenes are distinct polymorphs with the same space group. The phase transition from C2/c to P2₁/c symmetry in spodumene and LiScSi₂O₆ therefore occurs because the polymorphs stable at ambient conditions are isotypic to the high-temperature C2/c phases of clinopyroxenes such as pigeonite and clinoenstatite. Received: 22 December 1999 / Accepted: 7 June 2000     

Exsolution and coarsening in iron-free clinopyroxene during isothermal annealing

Exsolution and coarsening in Fe-free clinopyroxene of composition En_45.1Di_54.9 was studied at temperatures of 1300, 1200, and 1100°C, and annealing times between 10 min and 4320 h. Based on the wavelength of the exsolution lamellae, the exsolution process can be divided into exsolution sensu stricto and coarsening. During exsolution sensu stricto, the average wavelength of the “001” and “100” lamellae remains constant in contrast to the subsequent coarsening process. A progressive development of the microstructure is observed before coarsening which includes formation of island-like regions of dark contrast without phase separation, occurrence of pigeonite and diopside domains predominantly elongated along (100), formation of “100” exsolution lamellae, dissolution of the “100” lamellae, and predominant occurrence of “001” exsolution lamellae. All observations are in accordance with the exsolution mechanism of spinodal decomposition. After termination of the exsolution process, coarsening of the exsolution lamellae is observed. The “001” lamellae coarsen according to the rate law

     

Determination of cation distribution in (Co,Ni,Zn)2SiO4 olivine by synchrotron X-ray diffraction

 The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal diffraction method. The crystal data are (Co_0.377Ni_0.396Zn_0.227)₂SiO₄, M _r  = 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm³, Z = 4, D _x  = 4.864 g cm⁻³, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln [(A/B)_M1/(A/B)_M2] = −0.272 (IR _A -IR _B ) + 3.65 (EN _A −EN _B ), where IR (pm) and EN are ionic radius and electronegativity, respectively. Received: 8 April 1999 / Revised, accepted: 7 September 1999     

Ordering and exsolution processes in Or-rich alkali feldspar megacrysts from the Eldzhurtinskiy granite (Caucasus)

 The extremely young (2.5 Ma) I-type Eldzhurtinskiy granite complex (Central Caucasus) is uniform with respect to modal composition, major and trace element chemistries of bulk rocks and mineral phases. In contrast, it reveals two types of alkali feldspar megacrysts differing in tetrahedral Al-content (2t₁) and exsolution microtextures: 1. Alkali feldspar megacrysts (Or₇₀An₂Ab₂₈) from the top of the body consist of ideally coherent intergrowths of fine-scale regular Or- and Ab-rich lamellae. The exsolved K-feldspar host is monoclinic (2t₁=0.7), the exsolved Na-rich phase consists of Albite- and/or Pericline-twinned albite. 2. Megacrysts from greater depths have the same bulk composition, but the exsolved Ab-rich phase occurs in the form of optically visible, broad lamellae and patches of low albite. In addition, the K-rich host yields a higher degree of (Al, Si) ordering (2t₁=0.8). The evolution of the distinct types of megacrysts reflects differences in the cooling history within the upper and lower part of the granite body. The occurrence of the coherent lamellae in the megacrysts from the top of the body is attributed to exsolution under dry conditions during fast cooling, whereas coarsening of lamellae and formation of albite patches in the megacrysts from the lower part are caused by fluid-feldspar interaction. The transition zone in the body between the two types of megacrysts is sharp (in a depth interval of 100–200 m) and not related to shear zones. Received: 12 June 1995 / Accepted: 29 January 1996     

Hydrous olivine (Mg1? y? Fe2+y)2? x ?v x ? SiO4H2 x – a new DHMS phase of variable composition observed as nanometer-sized precipitations in mantle olivine

 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH⁻ or Fe³⁺. From these data it is concluded that there is a OH⁻- or Fe³⁺-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)^< _O−V^" _Me−(OH)^< _O}^↔, or {F e ^< _Fe −H _Me ^′}^↔ or {2F e ^< _Fe −V _Me ^"}^↔ point defect associates. The calculated theoretical compositions Mg_1.615Fe⁺² _0.135v_0.25SiO₄H_0.5 (Hy-2a) and Mg_1.54Fe²⁺ _0.12v_0.33SiO₄H_0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg_1-yFe²⁺ _y)_2−xv_xSiO₄H_2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO₄H₂] · 3[Mg_1.82Fe_0.18SiO₄] for Hy-2a, [MgSiO₄H₂] · 2[Mg_1.82Fe_0.18SiO₄] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001     

Pyroxene-Olivine-Quartz Assemblages in Rocks Associated with the Nain Anorthosite Massif, Labrador

Unusually iron-rich pyroxene and olivine occur in rocks associatedwith the Nain anorthosite massif, Labrador. Adamellite and granodioritecontain orthopyroxene (inverted from pigeonite) as iron-richas Ca₆Fe₈₂Mg₁₂; comparison with experimental data suggests aminimum pressure of crystallization of 5 kb. Some of these iron-richpyroxene crystals have broken down, apparently upon decreasingpressure, to yield intergrowths of less iron-rich orthopyroxene(near Ca₇Fe₇₂Mg₂₁), ferroaugite, fayalite (near Fo₉), and quartz.Other rocks, monzonites, contain pyroxenes with calcium-poorcores and ferroaugite rims, as well as crystals composed ofbroad lamellae of ferroaugite and orthopyroxene in sub-equalproportions. Analysis of one such crystal with unusually thinand closely spaced lamellae yielded a bulk composition of Ca₂₄Fe₅₈Mg₁₈.Such pyroxenes probably crystallized near or above the crestof the augite-pigeonite two-phase region, probably above 925°C. This high temperature suggests that the monzonites crystallizedfrom relatively dry magmas. If they represent a residual fractionderived from the same magma as the anorthosite, then that magmamust have been nearly anhydrous. Pigeonite rather than orthopyroxene was the primary magmaticCa-poor pyroxene in most of the Nain rocks studied here. Nucleationrates apparently were low under subsolidus conditions, and low-Capigeonite (Ca₂Fe₇₈Mg₂₀) is present in grains where orthopyroxenedid not nucleate as pigeonite cooled and exsolved ferroaugite.Iron-rich orthopyroxene (Ca₂Fe₇₉M₁₉) crystallized instead ofpigeonite in a Greenland quartz syenite that contains more abundanthydrous phases.     

Mechanisms of exsolution in sodic pyroxenes

The free energy curves for simple binary solid solutions with limited miscibility or atomic ordering have been combined to predict the phase relations and exsolution mechanisms for a system in which both ordering and exsolution are possible. The nature of the ordering process affects which exsolution mechanisms may be used. If the ordering is second (or higher) order in character then continuous mechanisms predominate and a ‘conditional spinodal’ (Alien and Cahn, 1976) can be described which operates between ordered and disordered end members. For a first order case, the ordered phase can only precipitate a disordered phase by nucleation and growth. Microstructures in omphacites observed by transmission electron microscopy include exsolution lamellae and antiphase domains and the relations between them in selected specimens have been used to interpret the exsolution mechanisms which operated under geological conditions. It appears that most omphacites undergo cation ordering, and then remain homogeneous or exsolve a disordered pyroxene by spinodal decomposition. The predominance of continuous mechanisms has been used to indicate that the C2/c→P2/n transformation may be second (or higher) order in character. A possible phase diagram for jadeite-augite is presented. It is based on the idea that there should be limited miscibility between the disordered end members at low temperatures and that the cation ordering at intermediate compositions (omphacite) is superimposed on a solvus. It is adequate to explain many of the observed microstructures and fits with petrographic evidence of broad two phase fields between impure jadeite and omphacite and between omphacite and sodic augite. The effect of adding acmite is analogous to increasing temperature so that the phase relations for jadeite-acmite-augite can also be predicted.